CN117659054B - Multi-arm organic photoelectric small molecule and preparation method and application thereof - Google Patents
Multi-arm organic photoelectric small molecule and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
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- 239000012074 organic phase Substances 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 14
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
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- 238000000926 separation method Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
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- 239000011149 active material Substances 0.000 claims description 5
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000000862 absorption spectrum Methods 0.000 abstract description 10
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 abstract description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 abstract description 6
- -1 cyclic fluorene diene Chemical class 0.000 abstract description 5
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 abstract description 4
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- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical class N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 abstract description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 3
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Abstract
The invention aims to provide a multi-arm organic photoelectric small molecule and a preparation method and application thereof, and belongs to the technical field of organic photoelectric materials. The organic photoelectric small molecule takes pyrene condensed [1,2,5] thiadiazole [3,4-g ] quinoxaline as a center, takes dithieno cyclic fluorene diene as a connection, and takes 2- (2-methylene-3-oxo-2, 3-dihydro-1H-indene-1-subunit) malononitrile derivatives as a tail end to form a multi-arm small molecule similar to a dimer structure. The band gap of the multi-arm organic photoelectric small molecular compound film prepared by the invention is less than or equal to 0.93eV, and the absorption spectrum range exceeds 1.3 mu m; the compound has a three-dimensional structure, can effectively inhibit excessive aggregation of molecules, and simultaneously forms effective accumulation among arms, so that the compound has good solubility in a conventional organic solvent, and can be used for preparing a high-quality film by a solution method. The organic photoelectric small molecule is taken as a receptor, and PCE10 is taken as a donor, so that the organic photoelectric small molecule can be well applied to the bulk heterojunction type organic light detector.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a multi-arm organic photoelectric small molecule, a preparation method and application thereof.
Background
The short wave infrared organic photodetector has good application prospect in the aspects of image sensing, biomedical detection and the likeScience2009, 325, 1665-1667；Adv. Mater. 2016, 28, 5969-5974). The organic photoelectric material can be synthesized from petrochemical byproducts, processed into films by room temperature solution, has the characteristics of intrinsic flexibility and the like, so that the organic photoelectric material has remarkable advantages in low cost and flexibility compared with the existing inorganic light detector, and has huge commercial development value and market in the futureAngew. Chem. Int. Ed. 2023, e202311686). In particular to a high-sensitivity organic light detector with detection wavelength exceeding 1100nm, which has important significance for biomedical detection imaging, night vision imaging, anti-counterfeiting security inspection, chip detection, industrial temperature measurement, internal damage detection of fruits and vegetables and the like which can be widely applied in the future.
The detection wavelength of the traditional silicon-based photodetector is cut off at 1100nm, and the detection wavelength of the InGaAs photodetector is 900-1700nm, but the InGaAs photodetector is quite expensive. The international high-performance organic photoelectric materials with detection wavelength exceeding 1100nm are very deficient (chem. Mater. 2019, 31, 6359-6379), and the development of the materials requires synergistic performance in the aspects of band gap narrowing, solubility, film forming property, crystallinity, high purity, energy level matching and the like, and is difficult to consider.
Therefore, the development of the organic photoelectric material with the detection wavelength exceeding 1100nm lays a solid foundation for the high-sensitivity organic light detector, and helps China to realize technical innovation and curve overtaking in the light detection field, thus having very practical significance.
Disclosure of Invention
Aiming at the problems existing in the background technology, the invention aims to provide a multi-arm organic photoelectric small molecule, and a preparation method and application thereof. The organic photoelectric small molecule takes pyrene condensed [1,2,5] thiadiazole [3,4-g ] quinoxaline as a center, takes dithieno cyclic fluorene diene as a connection, and takes 2- (2-methylene-3-oxo-2, 3-dihydro-1H-indene-1-subunit) malononitrile derivatives as a tail end to form a multi-arm small molecule similar to a dimer structure. The detection cut-off wavelength of the organic photoelectric detector prepared based on the organic photoelectric small molecules can reach 1.3 mu m.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a multi-arm organic photoelectric small molecule has a structural general formula shown in formula I:
(formula I),
in the formula I, Y 1 Is hydrogen, fluorine, chlorine or bromine, Y 2 Is hydrogen, fluorine, chlorine or bromine, R 1 Is a C1-C25 linear or branched alkyl group; x is a hydrogen atom, a tertiary butyl group or a C1-C25 straight-chain or branched-chain alkoxy group.
Further, the preparation method of the multi-arm organic photoelectric small molecule comprises the following steps:
step 1, synthesizing a first compound, wherein the specific process is as follows: dissolving a second compound and a third compound in a first organic solvent according to a molar ratio of 1 (2.5-6), adding a first catalyst, and reacting for 1-3 hours at 100-120 ℃ in an inert atmosphere; after the reaction is finished, naturally cooling to room temperature, adding a methanol solution, and removing the solvent by using rotary evaporation of an organic phase; finally, separating by a silica gel chromatographic column separation method to obtain a first compound;
step 2, synthesizing a fourth compound, wherein the specific process is as follows: adding a first compound, reduced iron powder and acetic acid into a second organic solvent, wherein the molar ratio of the first compound to the reduced iron powder to the acetic acid is 1 (8-16): (15-20), and the amounts of substances of the second organic solvent and the acetic acid are equal; then reacting for 1-2 hours at 60-70 ℃ in an inert atmosphere; after the reaction is finished, naturally cooling to room temperature, extracting and drying the obtained liquid product, and then removing the solvent by using organic phase rotary evaporation; finally separating by silica gel column chromatography to obtain a fourth compound;
step 3, synthesizing a fifth compound, wherein the specific process is as follows: mixing a sixth compound, a fourth compound obtained in the step 2 and acetic acid according to the molar ratio of (2.1-2.3) to (35-45), and reacting at 90-110 ℃ for 24-60 hours in an inert gas atmosphere; after the reaction is finished, naturally cooling to room temperature, extracting and drying the obtained liquid product, and then removing the solvent by using organic phase rotary evaporation; finally separating by silica gel column chromatography to obtain a fifth compound;
step 4, synthesizing a seventh compound, wherein the specific process is as follows: adding the fifth compound obtained in the step 3 and N, N-dimethylformamide into a third organic solvent, reacting for 1-2 hours at 0-5 ℃ in an inert gas atmosphere, dropwise adding phosphorus oxychloride in the reaction process, and keeping stirring; after the reaction is carried out for a period of time, the temperature is raised to room temperature, the reaction is carried out for 1 to 3 hours, after the reaction is finished, the temperature is naturally cooled to room temperature, the obtained liquid product is extracted and dried, and then the solvent is removed by using organic phase rotary evaporation; finally separating by silica gel column chromatography to obtain a seventh compound; wherein the molar ratio of the fifth compound to the N, N-dimethylformamide to the phosphorus oxychloride is 1 (20-50) (50-100);
step 5, synthesizing multi-arm organic photoelectric small molecules, wherein the specific process is as follows: adding the seventh compound, boron trifluoride diethyl etherate, propionic anhydride and the eighth compound obtained in the step 4 into a fourth organic solvent, wherein the molar ratio of the seventh compound, boron trifluoride diethyl etherate, propionic anhydride and the eighth compound is 1 (15-30): (8-15): (6-16); reacting for 4-36 hours at room temperature in an inert gas atmosphere; after the reaction is finished, naturally cooling to room temperature, adding methanol for precipitation, separating a solid product by combining suction filtration, separating and purifying by adopting a silica gel column chromatography, then recrystallizing and purifying, and finally separating and purifying by adopting the silica gel column chromatography to obtain the required multi-arm organic photoelectric micromolecule;
wherein the structural formula of the first compound is shown in formula II, the structural formula of the second compound is shown in formula III, the structural formula of the third compound is shown in formula IV, the structural formula of the fourth compound is shown in formula V, the structural formula of the fifth compound is shown in formula VI, the structural formula of the sixth compound is shown in formula VII, the structural formula of the seventh compound is shown in formula VIII, the structural formula of the eighth compound is shown in formula IX,
(formula II);
(formula III);
，
(formula IV);
，
(formula V);
，
(formula VI);
，
(formula VII);
，
(formula VIII);
，
(formula IX);
wherein in formula IV, R 1 Is defined as formula I; in the formula V, R 1 Is defined as formula I; in formula VI, R 1 X is defined as formula I; x in the formula VII is defined as formula I; in the formula VIII, R1 and X are defined as formula I; in formula IX, Y 1 、Y 2 The definition formula of (1) is as shown in formula I.
Further, in step 1, the organic solvent is toluene, chlorobenzene or o-dichlorobenzene, and the catalyst is Pd (PPh 3 ) 4 Or Pd (PPh) 3 ) 2 Cl 2 。
Further, the organic solvent in step 2 is preferably chloroform.
Further, in step 3, the reaction organic solvent is specifically tetrahydrofuran, dichloromethane or 1, 2-dichloroethane.
Further, the organic solvent in step 4 is preferably toluene.
The invention also provides application of the multi-arm organic photoelectric small molecule compound: the multi-arm organic photoelectric small molecular compound is used as an acceptor material, and the organic photoelectric detection device is prepared through solution spin coating.
Further, the organic photoelectric detection device is a diode type organic photoelectric detection device.
The mechanism of the invention is as follows: the strong electron-withdrawing unit and electron-donating unit are introduced to promote intramolecular charge transfer, and then the intermediate pyrene condensed [1,2,5] thiadiazole [3,4-g ] quinoxaline unit is used as a center to form a multi-arm small molecule similar to a dimer structure, and the multi-arm small molecule has more quinoid structure duty ratio than a single small molecule, so that the structure can prolong the conjugation length, thereby effectively reducing the band gap and widening the spectrum detection range.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. the multi-arm organic photoelectric small molecular compound takes pyrene condensed [1,2,5] thiadiazole [3,4-g ] quinoxaline as a center, dithieno cyclic fluorene diene as a connection, and 2- (2-methylene-3-oxo-2, 3-dihydro-1H-indene-1-subunit) malononitrile derivatives as a tail end to form a multi-arm small molecule similar to a dimer structure, so that the band gap can be effectively reduced, and the spectrum detection range can be widened. The band gap of the multi-arm organic photoelectric small molecular compound film prepared by the invention is less than or equal to 0.93 and eV, and the spectral cutoff wavelength is more than 1.3 mu m.
2. The multi-arm organic photoelectric molecule provided by the invention has a three-dimensional structure, can effectively inhibit excessive aggregation of molecules, and simultaneously forms effective accumulation among arms, so that the multi-arm organic photoelectric molecule has good solubility in a conventional organic solvent, and further can be used for preparing a high-quality film by a solution method. In addition, the organic photoelectric micromolecule is simple to synthesize, and the prepared material is high in purity.
3. The near infrared organic photoelectric small molecules can realize energy level matching with various conventional donor materials (such as PCE10, PBDB-T, PM, J52 and the like). Based on the obtained organic photoelectric micromolecules as receptors and PCE10 as a donor, a bulk heterojunction type organic light detector is prepared, the spectrum detection range of the bulk heterojunction type organic light detector can be covered by 0.4-1.3 mu m, the peak responsivity can reach 0.39A/W, the peak external quantum efficiency exceeds 50%, and the specific detection rate can reach 10 12 Jones, above. Therefore, the molecules have good application prospects in the aspect of preparing broad-spectrum short-wave infrared organic photodetectors.
Drawings
Fig. 1 is a synthetic route diagram of the near infrared organic photoelectric small molecule compound SM1 in example 1.
Fig. 2 is a synthetic route diagram of the near infrared organic photoelectric small molecule compound SM2 in example 2.
Fig. 3 is a solution absorption spectrum of the organic photoelectric molecule SM1 obtained in example 1 and the organic photoelectric molecule SM2 obtained in example 2.
Fig. 4 is a graph showing the thin film absorption spectra of the organic photoelectric molecule SM1 obtained in example 1 and the organic photoelectric molecule SM2 obtained in example 2.
Fig. 5 is a response curve of the light detecting device of the organic photoelectric molecule SM2 in example 3.
Fig. 6 is a graph showing the external quantum efficiency curve of the light detecting device of the organic photoelectric molecule SM2 in example 3.
Fig. 7 is a graph showing the specific detection rate of the organic photoelectric molecule SM2 in example 3.
Detailed Description
The present invention will be described in further detail with reference to the embodiments and the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
A multi-arm organic photoelectric small molecule has a structural general formula shown in formula I:
(formula I);
in the formula I, Y 1 Is hydrogen, fluorine, chlorine or bromine, Y 2 Is hydrogen, fluorine, chlorine or bromine, Y 1 And Y 2 The same or different; r is R 1 A linear or branched alkyl group of C1-C25; x is a hydrogen atom, a tertiary butyl group, a C1-C25 linear or branched alkoxy group.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
Example 1
The preparation method of the multi-arm organic photoelectric small molecule SM1 comprises the following steps:
step 1, synthesis of compound 3 (compound labeled 3 in fig. 1): 768mg of Compound 1 (compound labeled 1 in FIG. 1) and 3393mg of Compound 2 (compound labeled 2 in FIG. 1) were dissolved in 40ml of anhydrous toluene solvent under nitrogen atmosphere, and 84-mg Pd (PPh) 3 ) 4 A catalyst to obtain a mixed solution; heating the mixed solution to 110 o C, stirring and reacting for 1.5 hours; stopping heating after the reaction is finished, naturally cooling to room temperature, then adding 15ml of methanol solution, and removing the solvent by rotary evaporation of an organic phase; finally, petroleum ether is prepared according to the volume ratio: separating the mixture of dichloromethane with silica gel column chromatography to obtain compound 3 (1745 mg, 85%) with mass of 1745 mg and yield of 85% and MS (MALDI-TOF) m/z=1027; MS is a mass spectrum test, and m/z is a mass-to-charge ratio;
step 2, synthesis of compound 4 (compound numbered 4 in fig. 1): adding 323 mg of compound 3, 208mg of reduced iron powder and 10ml of acetic acid into 10ml of chloroform under nitrogen atmosphere, heating the mixed solution to 60 o C, stirring and reacting 1.5-h; stopping heating after the reaction is finished, and naturally cooling to room temperatureThen pouring the reaction solution into saturated sodium carbonate solution, extracting with dichloromethane, drying with anhydrous sodium sulfate, and removing the solvent by rotary evaporation of an organic phase; finally, petroleum ether is prepared according to the volume ratio: separating the mixture of dichloromethane and 7:1 as eluent by silica gel column chromatography to obtain compound 4 (210 mg, 70%), MS (MALDI-TOF) with m/z=967;
step 3, synthesis of compound 5 (compound numbered 5 in fig. 1): under nitrogen atmosphere, 336 mg of Compound 4, 40mg of pyrene-4, 5,9, 10-tetraketone were added to 25ml of acetic acid, and the mixed solution was heated to 100 o C, stirring reaction 48 h; stopping heating after the reaction is finished, naturally cooling to room temperature, pouring the reaction solution into saturated sodium carbonate solution, extracting with dichloromethane, drying with anhydrous sodium sulfate, and removing the solvent by adopting organic phase rotary evaporation; finally, petroleum ether is prepared according to the volume ratio: separating the mixture of dichloromethane and 6:1 as eluent by silica gel column chromatography to obtain compound 5 (222 mg, 61%), MS (MALDI-TOF) with m/z=2122;
step 4, synthesis of compound 6 (compound numbered 6 in fig. 1): 212.2mg of compound 5 and 219mg of N, N-dimethylformamide are dissolved in 10mL of 1, 2-dichloroethane under nitrogen atmosphere, then the mixed solution is cooled to 0 ℃ and 922g of phosphorus oxychloride is dripped under stirring, stirring is carried out for 2 hours, then the temperature is raised to room temperature, and stirring reaction 2 h is carried out at room temperature; after the reaction is finished, pouring the reaction solution into a saturated sodium carbonate solution, extracting with dichloromethane, washing with water for three times, and drying with anhydrous sodium sulfate; then removing the solvent by rotary evaporation of the organic phase; finally, separating by a silica gel chromatographic column separation method by taking dichloromethane as a leaching agent to obtain a solid product 6 (208 mg, 93%), wherein the solid product is MS (MALDI-TOF) with m/z=2234;
step 5, synthesizing SM1: under nitrogen atmosphere, 230 mg of 2- (3-oxo-2, 3-dihydro-1H-indene-1-subunit) malononitrile and 285 mg of compound 6 were dissolved in 13 ml of anhydrous toluene, then 370mg of boron trifluoride diethyl etherate and 1.3ml of propionic anhydride were added as catalysts, and the mixture was stirred at room temperature to react 24H; then, the reaction liquid is dripped into methanol solution to be separated out and filtered, and the obtained solid part is petroleum ether with the volume ratio: dichloromethane: the mixed solution of chloroform with the ratio of 1:2:0.02 is used as an eluent, a silica gel chromatographic column separation method is adopted to separate and obtain a product, the product is recrystallized by using a chloroform and acetonitrile system, and then petroleum ether with the volume ratio is used as follows: the product was isolated using a silica gel column eluting with a 1:4 mixture of dichloromethane to give SM1 (192 mg, 48%) and MS (MALDI-TOF) m/z=3083.
Example 2
The preparation method of the multi-arm organic photoelectric small molecule SM2 comprises the following steps:
the preparation process of step 1 and step 2 is the same as that of step 1 and step 2 in example 1;
step 3, synthesis of compound 5 (compound numbered 5 in fig. 2): under nitrogen atmosphere, 336 mg of Compound 4, 52mg of 2, 7-di-tert-butylpyrene-4, 5,9, 10-tetraketone were added to 25ml of acetic acid, and the mixed solution was heated to 100 o C, stirring reaction 48 h; stopping heating after the reaction is finished, naturally cooling to room temperature, pouring the reaction solution into saturated sodium carbonate solution, extracting with dichloromethane, drying with anhydrous sodium sulfate, and removing the solvent by adopting organic phase rotary evaporation; finally, petroleum ether is prepared according to the volume ratio: separating the mixture of dichloromethane and 6:1 as eluent by silica gel column chromatography to obtain compound 5 (231 mg, 61%), MS (MALDI-TOF) with m/z=2235;
step 4, synthesis of compound 6 (compound labeled 6 in fig. 2): under nitrogen atmosphere, 223.5mg of compound 5 and 219mg of N, N-dimethylformamide are dissolved in 10mL of 1, 2-dichloroethane, then the mixed solution is cooled to 0 ℃, 922g of phosphorus oxychloride is dropwise added under stirring, stirring is carried out for 2 hours, then the temperature is raised to room temperature, and stirring reaction is carried out at room temperature for 2 h; after the reaction is finished, pouring the reaction solution into a saturated sodium carbonate solution, extracting with dichloromethane, washing with water for three times, and drying with anhydrous sodium sulfate; then removing the solvent by rotary evaporation of the organic phase; finally, separating by a silica gel chromatographic column separation method by taking dichloromethane as a leaching agent to obtain a solid product 6 (283 mg, 93%), wherein the solid product is MS (MALDI-TOF) with m/z=2347;
step 5, synthesizing SM2: compound 6 of 230- (3-oxo-2, 3-dihydro-1H-indene-1-ylidene) malononitrile of mg and 305 mg was dissolved in an anhydrous toluene solution of 13 ml under nitrogen atmosphere, then 370mg of boron trifluoride diethyl etherate and 1.3ml of propionic anhydride were added as a catalyst, and the reaction was stirred at room temperature for 24H; then, the reaction liquid is dripped into methanol solution to be separated out and filtered, and the obtained solid part is petroleum ether with the volume ratio: separating the mixture with dichloromethane of 1:3 by silica gel chromatographic column separation to obtain product, cooling and recrystallizing the product with toluene to obtain SM2 (224 mg, 54%), MS (MALDI-TOF) with m/z=3195.
The organic photoelectromolecules SM1 and SM2 synthesized in example 1 and example 2 were measured, i.e., ultraviolet-visible-near infrared absorption spectra in the solution state and in the film state, respectively.
Testing in solution: firstly preparing the same 100 ml chloroform solution in 2 volumetric flasks, respectively, and then adding the organic photoelectric molecules SM1 and SM2 into the chloroform solution to make the concentration of the organic photoelectric small molecules 10 -5 mol/L concentration; the prepared solution was transferred to a quartz cuvette with an optical path length of 1 cm, and then the absorption spectrum in the solution state was tested, and the obtained absorption spectrum was shown in fig. 3.
Test in film state: the organic photoelectric molecules SM1 and SM2 are weighed, chloroform solution is respectively added to prepare solution with the concentration of 10mg/ml, then the solutions with the same volume are respectively spin-coated on a quartz plate by adopting a spin coating method to prepare films, then the absorption spectrum under the film state is tested, and the absorption spectrum obtained by normalization is shown in figure 4.
As can be seen from fig. 3, the absorption spectra of the two organic photoelectric small molecules in the solution state are both more than 1.2 μm, and the absorption spectra of the two organic photoelectric small molecules in the film state in fig. 4 are both more than 1.3 μm, which indicates that SM1 and SM2 are two organic photoelectric molecular materials with ultra-narrow band gaps.
Example 3
The preparation method of the organic light detector device based on the organic photoelectric micromolecule SM2 comprises the following specific preparation processes:
step 1, sequentially ultrasonically cleaning transparent conductive glass with ITO (indium tin oxide) by deionized water, acetone and isopropanol for 15 minutes, and then treating the surface of a substrate by ozone;
step 2, coating a ZnO modified layer with the thickness of 30nm on the surface of the ITO;
step 3, preparing an active material layer by taking an organic photoelectric molecule SM2 as an acceptor material and PCE10 as a donor material:
mixing an organic photoelectric molecule SM2 and PCE10 according to a mass ratio of 1:1, and then dissolving the mixed solution in a chloroform organic solvent to prepare a precursor solution with a concentration of 20 mg/mL; uniformly spin-coating the precursor solution on the surface of the ZnO modified layer at the rotating speed of 600-4000 rpm in a glove box to obtain an active material layer with the thickness of 200 nm;
step 4, at 2×10 -6 Evaporating MoOx on the surface of the active material layer under the vacuum degree of the support to form a 10nm modification layer;
step 5, at 2×10 -6 Evaporating Ag onto the MoOx modified layer under vacuum degree to form an electrode with thickness of 100nm, thereby obtaining the organic photodetector device with device structure of ITO/ZnO/SM 2: PCE 10/MoOx/Ag.
The organic photoelectric detector prepared in this example was tested for responsivity, external quantum efficiency and specific detection rate performance, and the test results are shown in fig. 5, 6 and 7, respectively.
As can be seen from FIG. 5, the responsivity peak of the organic photodetector device can reach 0.39A/W, the external quantum efficiency peak of FIG. 6 exceeds 50%, the organic photodetector device has better light detection response to near infrared light, the specific detection rate of the organic photodetector device in the specific detection rate calculation of FIG. 7 can reach 10 in the specific detection range of 0.4-1.3 μm 12 Above Jones, the molecules are fully demonstrated to have good application prospect in the aspect of preparing a broad-spectrum short-wave infrared organic photoelectric detector, and good photoelectric detection performance can be obtained.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.
Claims (8)
1. The multi-arm organic photoelectric small molecule is characterized in that the structural general formula of the multi-arm organic photoelectric small molecule is shown as formula I:
，
(formula I);
in the formula I, Y 1 Is hydrogen, fluorine, chlorine or bromine, Y 2 Is hydrogen, fluorine, chlorine or bromine, R 1 Is a C1-C25 linear or branched alkyl group; x is a hydrogen atom or a tert-butyl group.
2. The preparation method of the multi-arm organic photoelectric small molecule is characterized by comprising the following steps of:
step 1, synthesizing a first compound, wherein the specific process is as follows: dissolving a second compound and a third compound in a first organic solvent according to a molar ratio of 1 (2.5-6), adding a first catalyst, and reacting for 1-3 hours at 100-120 ℃ in an inert atmosphere; after the reaction is finished, naturally cooling to room temperature, adding a methanol solution, and removing the solvent by using rotary evaporation of an organic phase; finally, separating by a silica gel chromatographic column separation method to obtain a first compound;
step 2, synthesizing a fourth compound, wherein the specific process is as follows: adding a first compound, reduced iron powder and acetic acid into a second organic solvent, wherein the molar ratio of the first compound to the reduced iron powder to the acetic acid is 1 (8-16): (15-20), and the amounts of substances of the second organic solvent and the acetic acid are equal; then reacting for 1-2 hours at 60-70 ℃ in an inert atmosphere; after the reaction is finished, naturally cooling to room temperature, extracting and drying the obtained liquid product, and then removing the solvent by using organic phase rotary evaporation; finally separating by silica gel column chromatography to obtain a fourth compound;
step 3, synthesizing a fifth compound, wherein the specific process is as follows: mixing a sixth compound, a fourth compound obtained in the step 2 and acetic acid according to the molar ratio of (2.1-2.3) to (35-45), and reacting at 90-110 ℃ for 24-60 hours in an inert gas atmosphere; after the reaction is finished, naturally cooling to room temperature, extracting and drying the obtained liquid product, and then removing the solvent by using organic phase rotary evaporation; finally separating by silica gel column chromatography to obtain a fifth compound;
step 4, synthesizing a seventh compound, wherein the specific process is as follows: adding the fifth compound obtained in the step 3 and N, N-dimethylformamide into a third organic solvent, reacting for 1-2 hours at 0-5 ℃ in an inert gas atmosphere, dropwise adding phosphorus oxychloride in the reaction process, and keeping stirring; after the reaction is carried out for a period of time, the temperature is raised to room temperature, the reaction is carried out for 1 to 3 hours, after the reaction is finished, the temperature is naturally cooled to room temperature, the obtained liquid product is extracted and dried, and then the solvent is removed by using organic phase rotary evaporation; finally separating by silica gel column chromatography to obtain a seventh compound; wherein the molar ratio of the fifth compound to the N, N-dimethylformamide to the phosphorus oxychloride is 1 (20-50) (50-100);
step 5, synthesizing multi-arm organic photoelectric small molecules, wherein the specific process is as follows: adding the seventh compound, boron trifluoride diethyl etherate, propionic anhydride and the eighth compound obtained in the step 4 into a fourth organic solvent, wherein the molar ratio of the seventh compound, boron trifluoride diethyl etherate, propionic anhydride and the eighth compound is 1 (15-30): (8-15): (6-16); reacting for 4-36 hours at room temperature in an inert gas atmosphere; naturally cooling to room temperature after the reaction is finished, adding methanol for precipitation, separating a solid product by combining suction filtration, separating and purifying by adopting a silica gel column chromatography, then recrystallizing and purifying, and finally separating and purifying by adopting the silica gel column chromatography to obtain the multi-arm organic photoelectric micromolecule as defined in claim 1;
wherein the structural formula of the first compound is shown in formula II, the structural formula of the second compound is shown in formula III, the structural formula of the third compound is shown in formula IV, the structural formula of the fourth compound is shown in formula V, the structural formula of the fifth compound is shown in formula VI, the structural formula of the sixth compound is shown in formula VII, the structural formula of the seventh compound is shown in formula VIII, the structural formula of the eighth compound is shown in formula IX,
(formula II);
(formula III);
，
(formula IV);
，
(formula V);
，
(formula VI);
，
(formula VII);
，
(formula VIII);
，
(formula IX);
wherein in formula IV, R 1 Is defined as formula I; in the formula V, R 1 Is defined as formula I; in formula VI, R 1 X is defined as formula I; x in the formula VII is defined as formula I; in the formula VIII, R1 and X are defined as formula I; in formula IX, Y 1 、Y 2 The definition formula of (1) is as shown in formula I.
3. The process according to claim 2, wherein in step 1, the first organic solvent is toluene, chlorobenzene or o-dichlorobenzene, and the first catalyst is Pd (PPh 3 ) 4 Or Pd (PPh) 3 ) 2 Cl 2 。
4. The method of claim 2, wherein in step 2, the second organic solvent is chloroform.
5. The process according to claim 2, wherein in step 4, the third organic solvent is tetrahydrofuran, dichloromethane or 1, 2-dichloroethane.
6. The method of claim 2, wherein in step 5, the fourth organic solvent is toluene.
7. The photoelectric detector comprises a substrate, a first modification layer, an active material layer, a second modification layer and an electrode layer from bottom to top in sequence; the preparation method is characterized in that the active material layer is made of the multi-arm organic photoelectric small molecule obtained by the preparation method according to any one of claims 2-6.
8. The photodetector of claim 7 wherein said photodetector is a diode-type organic photodetector.
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